Preparation of Unsymmetrical Diaryl Selenides via S<sub>N</sub>Ar Reactions in η<sup>6</sup>-Chloroarene Transition Metal Complexes
作者:Andrei A. Vasil'ev、Lars Engman、J. Peter Storm、Carl-Magnus Andersson
DOI:10.1021/om980948q
日期:1999.3.1
Unsymmetrical diaryl selenides were prepared by nucleophilic displacement of chloride with areneselenolates in η6-(arene) Cr(CO)3, FeCpPF6, and Mn(CO)3PF6 complexes. Areneselenolates were conveniently generated in situ by hydrazine reduction of the corresponding diaryl diselenides and reacted with chloroarene Cr(CO)3 complexes in dimethyl sulfoxide at 70 °C. The reactivity of the cationic FeCpPF6 and
不对称的二芳基硒化物是通过在烯基6-(亚芳基)Cr(CO)3,FeCpPF 6和Mn(CO)3 PF 6络合物中将苯磺酸与苯磺酸硒酸酯进行亲核置换制备的。通过肼还原相应的二芳基二硒化物方便地在原位生成芳烃硒酸酯,并使其与氯芳烃Cr(CO)3络合物在二甲亚砜中于70°C反应。阳离子FeCpPF 6和Mn(CO)3 PF 6的反应性氯芳烃的配合物要高得多,在环境温度下用乙醇提供的取代产物是由硼氢化钠还原生成的戊二烯酸酯。分离出中间(芳基硒代)芳烃铬和铁配合物,并通过77 Se NMR表征。与游离的二芳基硒化物相比,络合会导致20-45 ppm的低场偏移。